Compound and transition metal compound

ABSTRACT

The present invention relates to a novel ligand compound represented by Formula 1 and a novel transition metal compound represented by Formula 2, and the novel ligand compound and transition metal compound according to the present invention has high comonomer incorporation effect in the preparation of an olefinic polymer having a low density and a high molecular weight, and thus can be usefully used as a catalyst for a polymerization reaction.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a divisional of U.S. application Ser. No.15/749,309, filed Jan. 31, 2018 which is a national phase entry under 35U.S.C. § 371 of International Application No. PCT/KR2017/001503, filedFeb. 10, 2017, which claims priority to Korean Patent Application No.10-2016-0016517, filed Feb. 12, 2016 and Korean Patent Application No.10-2017-0018307, filed Feb. 9, 2017, the disclosures of which areincorporated herein by reference

TECHNICAL FIELD

The present invention relates to a novel ligand compound and transitionmetal compound.

BACKGROUND ART

Metallocene catalysts for olefin polymerization have been developed fora long time. Metallocene compounds are generally activated byaluminoxane, borane, borate or other activators and used. For example,aluminoxane is used as an activator for a metallocene compound having aligand including a cyclopentadienyl group and two sigma chlorideligands. A case in which, when a chloride group of the metallocenecompound is replaced with another ligand (e.g., a benzyl ortrimethylsilyl methyl group (—CH₂SiMe₃)), the effect of increasingcatalytic activity or the like is exhibited, has been reported.

[Me₂Si(Me₄C₅)NtBu]TiCl₂ (constrained-geometry catalyst, CGC) wasdisclosed by U.S. Pat. No. 5,064,802 of the Dow Co. in the early 1990s,and excellent aspects of the CGC in the copolymerization reaction ofethylene and an alpha-olefin may be summarized in the following twopoints when compared to known metallocene catalysts: (1) Even at a highpolymerization temperature, high activity is shown and a polymer havinga high molecular weight is produced, and (2) the copolymerization degreeof an alpha-olefin having large steric hindrance such as 1-hexene and1-octene is excellent.

Further, as various properties of the CGC during a polymerizationreaction are gradually known, efforts of synthesizing the derivativesthereof and using them as a polymerization catalyst have been activelyconducted in academia and industry.

As one approach, the synthesis of a metal compound introducing variousbridges instead of a silicon bridge and a nitrogen substituent and thepolymerization thereof has been conducted. In representative metalcompounds known until now, phosphorous, ethylene or propylene,methylidene or methylene bridges are introduced instead of the siliconbridge of a CGC structure, but excellent results in terms ofpolymerization activity, copolymerization performance or the like couldnot be obtained by applying to ethylene polymerization orcopolymerization with an alpha-olefin when compared to those obtained byapplying the CGC.

As another approach, many compounds including an oxido ligand instead ofthe amido ligand of the CGC have been synthesized, and attempts atpolymerization using them have been conducted to some extent.

Further, a variety of asymmetric non-crosslinked metallocenes have beendeveloped. For example, (cyclopentadienyl)(indenyl) and(cyclopentadienyl)(fluorenyl) metallocene, (substitutedindenyl)(cyclopentadienyl) metallocene and the like are known.

However, in view of commercial use, the catalyst compositions of thenon-crosslinked metallocenes do not sufficiently exhibit thepolymerization activity of olefins, and polymerization of a polyolefinhaving a high molecular weight is difficult.

DISCLOSURE Technical Problem

An object of the present invention is to provide a novel ligandcompound.

Another object of the present invention is to provide a novel transitionmetal compound.

Technical Solution

In order to solve the above problem, the present invention provides aligand compound represented by the following Formula 1:

in Formula 1, R₁ to R₉ each independently represent hydrogen, a silyl,an alkyl having 1 to 20 carbon atoms, an alkenyl having 2 to 20 carbonatoms, an aryl having 6 to 20 carbon atoms, an alkylaryl having 7 to 20carbon atoms, an arylalkyl having 7 to 20 carbon atoms or a metalloidradical of a Group 14 metal substituted with a hydrocarbyl having 1 to20 carbon atoms; two or more adjacent groups of the R₁ to R₈ may beconnected to each other to form an aliphatic ring having 5 to 20 carbonatoms or an aromatic ring having 6 to 20 carbon atoms; the aliphaticring or aromatic ring may be substituted with a halogen, an alkyl having1 to 20 carbon atoms, an alkenyl having 2 to 20 carbon atoms or an arylhaving 6 to 20 carbon atoms; and n is 1 or 2.

Further, in order to solve another problem, the present inventionprovides a transition metal compound represented by the followingFormula 2:

in Formula 2, R₁ to R₉ each independently represent hydrogen, a silyl,an alkyl having 1 to 20 carbon atoms, an alkenyl having 2 to 20 carbonatoms, an aryl having 6 to 20 carbon atoms, an alkylaryl having 7 to 20carbon atoms, an arylalkyl having 7 to 20 carbon atoms or a metalloidradical of a Group 14 metal substituted with a hydrocarbyl having 1 to20 carbon atoms; two or more adjacent groups of the R₁ to R₈ may beconnected to each other to form an aliphatic ring having 5 to 20 carbonatoms or an aromatic ring having 6 to 20 carbon atoms; the aliphaticring or aromatic ring may be substituted with a halogen, an alkyl having1 to 20 carbon atoms, an alkenyl having 2 to 20 carbon atoms or an arylhaving 6 to 20 carbon atoms; and n is 1 or 2; Q¹ and Q² eachindependently represent hydrogen, a halogen, an alkyl having 1 to 20carbon atoms, an alkenyl having 2 to 20 carbon atoms, an aryl having 6to 20 carbon atoms, an alkylaryl having 6 to 20 carbon atoms, anarylalkyl having 7 to 20 carbon atoms, an alkylamido having 1 to 20carbon atoms, an arylamido having 6 to 20 carbon atoms, or an alkylidenehaving 1 to 20 carbon atoms; and M is Ti, Zr or Hf.

Advantageous Effects

The novel ligand compound and transition metal compound according to thepresent invention has a high comonomer incorporation effect in thepreparation of an olefinic polymer having a low density and a highmolecular weight, and thus can be usefully used as a catalyst forpolymerization reactions.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in more detail toallow for a clearer understanding of the present invention.

It will be understood that words or terms used in the specification andclaims shall not be interpreted as the meaning defined in commonly useddictionaries. It will be further understood that the words or termsshould be interpreted as having a meaning that is consistent with theirmeaning in the context of the relevant art and the technical idea of theinvention, based on the principle that an inventor may properly definethe meaning of the words or terms to best explain the invention.

A ligand compound of the present invention is represented by thefollowing Formula 1.

in Formula 1, R₁ to R₉ each independently represent hydrogen, a silyl,an alkyl having 1 to 20 carbon atoms, an alkenyl having 2 to 20 carbonatoms, an aryl having 6 to 20 carbon atoms, an alkylaryl having 7 to 20carbon atoms, an arylalkyl having 7 to 20 carbon atoms or a metalloidradical of a Group 14 metal substituted with a hydrocarbyl having 1 to20 carbon atoms; two or more adjacent groups of the R₁ to R₈ may beconnected to each other to form an aliphatic ring having 5 to 20 carbonatoms or an aromatic ring having 6 to 20 carbon atoms; the aliphaticring or aromatic ring may be substituted with a halogen, an alkyl having1 to 20 carbon atoms, an alkenyl having 2 to 20 carbon atoms or an arylhaving 6 to 20 carbon atoms; and n is 1 or 2.

Further, in Formula 1, R₁ to R₉ each may independently representhydrogen, an alkyl having 1 to 20 carbon atoms, an aryl having 6 to 20carbon atoms, an alkylaryl having 7 to 20 carbon atoms, or an arylalkylhaving 7 to 20 carbon atoms; two or more adjacent groups of the R₁ to R₈may be connected to each other to form an aliphatic ring having 5 to 20carbon atoms or an aromatic ring having 6 to 20 carbon atoms; and thealiphatic ring or aromatic ring may be substituted with a halogen, analkyl having 1 to 20 carbon atoms, or an aryl having 6 to 20 carbonatoms.

In an example of the present invention, the ligand compound of Formula 1may be one of the following compounds:

Furthermore, the transition metal compound according to the presentinvention may be represented by the following Formula 2.

in Formula 2, R₁ to R₉ each independently represent hydrogen, a silyl,an alkyl having 1 to 20 carbon atoms, an alkenyl having 2 to 20 carbonatoms, an aryl having 6 to 20 carbon atoms, an alkylaryl having 7 to 20carbon atoms, an arylalkyl having 7 to 20 carbon atoms or a metalloidradical of a Group 14 metal substituted with a hydrocarbyl having 1 to20 carbon atoms; two or more adjacent groups of the R₁ to R₈ may beconnected to each other to form an aliphatic ring having 5 to 20 carbonatoms or an aromatic ring having 6 to 20 carbon atoms; the aliphaticring or aromatic ring may be substituted with a halogen, an alkyl having1 to 20 carbon atoms, an alkenyl having 2 to 20 carbon atoms or an arylhaving 6 to 20 carbon atoms; n is 1 or 2; Q¹ and Q² each independentlyrepresent hydrogen, a halogen, an alkyl having 1 to 20 carbon atoms, analkenyl having 2 to 20 carbon atoms, an aryl having 6 to 20 carbonatoms, an alkylaryl having 6 to 20 carbon atoms, an arylalkyl having 7to 20 carbon atoms, an alkylamido having 1 to 20 carbon atoms, anarylamido having 6 to 20 carbon atoms, or an alkylidene having 1 to 20carbon atoms; and M is Ti, Zr or Hf.

Further, in Formula 2, Q¹ and Q² each may independently representhydrogen, a halogen, an alkyl having 1 to 20 carbon atoms, an arylhaving 6 to 20 carbon atoms, an alkylaryl having 6 to 20 carbon atoms,or an arylalkyl having 7 to 20 carbon atoms.

Further, in Formula 2, R₁ to R₉ each may independently representhydrogen, an alkyl having 1 to 20 carbon atoms, an aryl having 6 to 20carbon atoms, an alkylaryl having 7 to 20 carbon atoms, or an arylalkylhaving 7 to 20 carbon atoms; two or more adjacent groups of the R₁ to R₈may be connected to each other to form an aliphatic ring having 5 to 20carbon atoms or an aromatic ring having 6 to 20 carbon atoms; thealiphatic ring or aromatic ring may be substituted with a halogen, analkyl having 1 to 20 carbon atoms, or an aryl having 6 to 20 carbonatoms.

In an example of the present invention, the compound of Formula 2 may beone of the following compounds:

Further, in addition to Formulas 2a to 2v, each of specific substituentsof the compound of Formula 2 and a combination thereof are shown in thefollowing Tables 1 to 5.

TABLE 1 no n M Q¹ Q² R₁ R₂ R₃ R₄ R₅ R₆ R₇ R₈ R₉ 1 1 Hf Cl ClDiisopropylphenyl Phenyl H H H H H H —CH₃ 2 1 Hf Cl Cl DiisopropylphenylIsopropylphenyl H H H H H H —CH₃ 3 1 Zr Cl Cl Diisopropylphenyl Phenyl HH H H H H —CH₃ 4 1 Zr Cl Cl Diisopropyphenyll Isopropylphenyl H H H H HH —CH₃ 5 2 Zr Cl Cl Diisopropylphenyl Phenyl H H H H H H H 6 2 Zr Cl ClDiisopropylphenyl Isopropylphenyl H H H H H H H 7 2 Zr Cl ClDiisopropylphenyl Phenyl H H H H H H —CH₃ 8 2 Zr Cl Cl DiisopropylphenylIsopropylphenyl H H H H H H —CH₃ 9 2 Zr Cl Cl Diisopropylphenyl BiphenylH H H H H H —CH₃ 10 2 Zr Cl Cl t-butyl Phenyl H H H H H H —CH₃ 11 2 ZrCl Cl t-butyl Isopropylphenyl H H H H H H —CH₃ 12 2 Zr Cl ClDiisopropylphenyl Naphthyl H H H H H H —CH₃ 13 2 Zr Cl ClDiisopropylphenyl t- H H H H H H —CH₃ butylphenyl 14 2 Hf Cl ClDiisopropylphenyl Phenyl H H H H H H H 15 2 Hf Cl Cl DiisopropylphenylIsopropylphenyl H H H H H H H 16 2 Hf Cl Cl Diisopropylphenyl Phenyl H HH H H H —CH₃ 17 2 Hf Cl Cl Diisopropylphenyl Isopropylphenyl H H H H H H—CH₃ 18 2 Hf Cl Cl Diisopropylphenyl Biphenyl H H H H H H —CH₃ 19 2 HfCl Cl t-butyl Phenyl H H H H H H —CH₃ 20 2 Hf Cl Cl t-butylIsopropylphenyl H H H H H H —CH₃ 21 2 Hf Cl Cl DiisopropylphenylNaphthyl H H H H H H —CH₃ 22 2 Hf Cl Cl Diisopropylphenyl t- H H H H H H—CH₃ butylphenyl

TABLE 2 no n M Q¹ Q² R₁ R₂ R₃ R₄ R₅ R₆ R₇ R₈ R₉ 23 1 Hf Me Me PhenylDiisopropylphenyl H H H H H H —CH₃ 24 1 Hf Me Me IsopropylphenylDiisopropylphenyl H H H H H H —CH₃ 25 1 Hf Me Me PhenylDiisopropylphenyl H H H H H H H 26 1 Hf Me Me IsopropylphenylDiisopropylphenyl H H H H H H H 27 1 Hf Me Me Phenyl Phenyl H H H H H H—CH₃ 28 1 Hf Me Me Diisopropylphenyl Diisopropylphenyl H H H H H H —CH₃29 1 Hf Me Me Isopropylphenyl Isopropylphenyl H H H H H H —CH3 30 1 HfMe Me Isopropylphenyl Phenyl H H H H H H —CH₃ 31 1 Hf Me Me PhenylIsopropylphenyl H H H H H H —CH₃ 32 1 Hf Me Me Phenyl Phenyl H H H H H HH 33 1 Hf Me Me Diisopropylphenyl Diisopropylphenyl H H H H H H H 34 1Hf Me Me Isopropylphenyl Isopropylphenyl H H H H H H H 35 1 Hf Me MeIsopropylphenyl Phenyl H H H H H H H 36 1 Hf Me Me PhenylIsopropylphenyl H H H H H H H 37 1 Hf Me Me t-butyl Phenyl H H H H H H—CH₃ 38 1 Hf Me Me t-butyl Isopropylphenyl H H H H H H —CH₃ 39 1 Hf MeMe Diisopropylphenyl Naphthyl H H H H H H —CH₃ 40 1 Hf Me MeDiisopropylphenyl t- H H H H H H —CH₃ butylphenyl 41 1 Hf Me Me t-butylPhenyl H H H H H H H 42 1 Hf Me Me t-butyl Isopropylphenyl H H H H H H H43 1 Hf Me Me Diisopropylphenyl Naphthyl H H H H H H H

TABLE 3 no n M Q¹ Q² R₁ R₂ R₃ R₄ R₅ R₆ R₇ R₈ R₉ 44 1 Hf Cl ClDiisopropylphenyl t- H H H H H H H butylphenyl 45 1 Hf Cl Cl PhenylDiisopropylphenyl H H H H H H —CH₃ 46 1 Hf Cl Cl IsopropylphenylDiisopropylphenyl H H H H H H —CH₃ 47 1 Hf Cl Cl PhenylDiisopropylphenyl H H H H H H H 48 1 Hf Cl Cl IsopropylphenylDiisopropylphenyl H H H H H H H 49 1 Hf Cl Cl Phenyl Phenyl H H H H H H—CH₃ 50 1 Hf Cl Cl Diisopropylphenyl Diisopropylphenyl H H H H H H —CH₃51 1 Hf Cl Cl Isopropylphenyl Isopropylphenyl H H H H H H —CH₃ 52 1 HfCl Cl Isopropylphenyl Phenyl H H H H H H —CH₃ 53 1 Hf Cl Cl PhenylIsopropylphenyl H H H H H H —CH₃ 54 1 Hf Cl Cl Phenyl Phenyl H H H H H HH 55 1 Hf Cl Cl Diisopropylphenyl Diisopropylphenyl H H H H H H H 56 1Hf Cl Cl Isopropylphenyl Isopropylphenyl H H H H H H H 57 1 Hf Cl ClIsopropylphenyl Phenyl H H H H H H H 58 1 Hf Cl Cl PhenylIsopropylphenyl H H H H H H H 59 1 Hf Cl Cl t-butyl Phenyl H H H H H H—CH₃ 60 1 Hf Cl Cl t-butyl Isopropylphenyl H H H H H H —CH₃ 61 1 Hf ClCl Diisopropylphenyl Naphthyl H H H H H H —CH₃ 62 1 Hf Cl ClDiisopropylphenyl t- H H H H H H —CH₃ butylphenyl 63 1 Hf Cl Cl t-butylPhenyl H H H H H H H 64 1 Hf Cl Cl t-butyl Isopropylphenyl H H H H H H H65 1 Hf Cl Cl Diisopropylphenyl Naphthyl H H H H H H H 66 1 Hf Cl ClDiisopropylphenyl t- H H H H H H H butylphenyl

TABLE 4 no n M Q¹ Q² R₁ R₂ R₃ R₄ R₅ R₆ R₇ R₈ R₉ 67 2 Hf Me Me PhenylDiisopropylphenyl H H H H H H —CH₃ 68 2 Hf Me Me IsopropylphenylDiisopropylphenyl H H H H H H —CH₃ 69 2 Hf Me Me PhenylDiisopropylphenyl H H H H H H H 70 2 Hf Me Me IsopropylphenylDiisopropylphenyl H H H H H H H 71 2 Hf Me Me Phenyl Phenyl H H H H H H—CH₃ 72 2 Hf Me Me Diisopropylphenyl Diisopropylphenyl H H H H H H —CH₃73 2 Hf Me Me Isopropylphenyl Isopropylphenyl H H H H H H —CH₃ 74 2 HfMe Me Isopropylphenyl Phenyl H H H H H H —CH₃ 75 2 Hf Me Me PhenylIsopropylphenyl H H H H H H —CH₃ 76 2 Hf Me Me Phenyl Phenyl H H H H H HH 77 2 Hf Me Me Diisopropylphenyl Diisopropylphenyl H H H H H H H 78 2Hf Me Me Isopropylphenyl Isopropylphenyl H H H H H H H 79 2 Hf Me MeIsopropylphenyl Phenyl H H H H H H H 80 2 Hf Me Me PhenylIsopropylphenyl H H H H H H H 81 2 Hf Me Me t-butyl Phenyl H H H H H H—CH₃ 82 2 Hf Me Me t-butyl Isopropylphenyl H H H H H H —CH₃ 83 2 Hf MeMe Diisopropylphenyl Naphthyl H H H H H H —CH₃ 84 2 Hf Me MeDiisopropylphenyl t- H H H H H H —CH₃ butylphenyl 85 2 Hf Me Me t-butylPhenyl H H H H H H H 86 2 Hf Me Me t-butyl Isopropylphenyl H H H H H H H87 2 Hf Me Me Diisopropylphenyl Naphthyl H H H H H H H 88 2 Hf Me MeDiisopropylphenyl t- H H H H H H H butylphenyl 89 2 Hf Cl Cl PhenylDiisopropylphenyl H H H H H H —CH₃ 90 2 Hf Cl Cl IsopropylphenylDiisopropylphenyl H H H H H H —CH₃

TABLE 5 no n M Q¹ Q² R₁ R₂ R₃ R₄ R₅ R₆ R₇ R₈ R₉ 91 2 Hf Cl Cl PhenylDiisopropylphenyl H H H H H H H 92 2 Hf Cl Cl IsopropylphenylDiisopropylphenyl H H H H H H H 93 2 Hf Cl Cl Phenyl Phenyl H H H H H H—CH₃ 94 2 Hf Cl Cl Diisopropylphenyl Diisopropylphenyl H H H H H H —CH₃95 2 Hf Cl Cl Isopropylphenyl Isopropylphenyl H H H H H H —CH₃ 96 2 HfCl Cl Isopropylphenyl Phenyl H H H H H H —CH₃ 97 2 Hf Cl Cl PhenylIsopropylphenyl H H H H H H —CH₃ 98 2 Hf Cl Cl Phenyl Phenyl H H H H H HH 99 2 Hf Cl Cl Diisopropylphenyl Diisopropylphenyl H H H H H H H 100 2Hf Cl Cl Isopropylphenyl Isopropylphenyl H H H H H H H 101 2 Hf Cl ClIsopropylphenyl Phenyl H H H H H H H 102 2 Hf Cl Cl PhenylIsopropylphenyl H H H H H H H 103 2 Hf Cl Cl t-butyl Phenyl H H H H H H—CH₃ 104 2 Hf Cl Cl t-butyl Isopropylphenyl H H H H H H —CH₃ 105 2 Hf ClCl Diisopropylphenyl Naphthyl H H H H H H —CH₃ 106 2 Hf Cl ClDiisopropylphenyl t- H H H H H H —CH₃ butylphenyl 107 2 Hf Cl Cl t-butylPhenyl H H H H H H H 108 2 Hf Cl Cl t-butyl Isopropylphenyl H H H H H HH 109 2 Hf Cl Cl Diisopropylphenyl Naphthyl H H H H H H H 110 2 Hf Cl ClDiisopropylphenyl t- H H H H H H H butylphenyl

The definition of each substituent used in the present specification isdescribed in detail as follows.

The term “halogen” used in the present specification, unless otherwisespecified, refers to fluorine, chlorine, bromine and iodine.

The term “alkyl” used in the present specification, unless otherwisespecified, refers to a linear or branched hydrocarbon residue.

The term “alkenyl” used in the present specification, unless otherwisespecified, refers to a linear or branched alkenyl group.

The branched chain may be an alkyl having 1 to 20 carbon atoms; analkenyl having 2 to 20 carbon atoms; an aryl having 6 to 20 carbonatoms; an alkylaryl having 7 to 20 carbon atoms; or an arylalkyl having7 to 20 carbon atoms.

According to an example of the present invention, the silyl groupincludes trimethyl silyl, triethyl silyl, tripropyl silyl, tributylsilyl, trihexyl silyl, triisopropyl silyl, triisobutyl silyl, triethoxysilyl, triphenyl silyl, tris(trimethylsilyl) silyl, but is not limitedthereto.

According to an example of the present invention, the aryl grouppreferably has 6 to 20 carbon atoms, and specifically includes phenyl,naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl and the like,but is not limited thereto.

The alkylaryl group refers to an aryl group substituted with the alkylgroup.

The arylalkyl group refers to an alkyl group substituted with the arylgroup.

The ring (or a heterocyclic group) refers to a monovalent aliphatic oraromatic hydrocarbon group which has a ring atom with 5 to 20 carbonatoms and contains one or more heteroatoms, and may be a single ring ora condensed ring of two or more rings. Further, the heterocyclic groupmay be unsubstituted or substituted with an alkyl group. Examplesthereof include indoline, tetrahydroquinoline and the like, but thepresent invention is not limited thereto.

The alkylamino group refers to an amino group substituted with the alkylgroup, and includes a dimethylamino group, a diethylamino group and thelike, but is not limited thereto.

According to an embodiment of the present invention, the aryl grouppreferably has 6 to 20 carbon atoms, and specifically includes phenyl,naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl and the like,but is not limited thereto.

The ligand compound of the present invention may be prepared by thefollowing method, and specifically, the ligand compound represented byFormula 1 of the present invention may be prepared by a method includingthe following steps: (1) reacting a compound of the following Formula 3with a compound of the following Formula 4 to prepare a compound of thefollowing Formula 5; and (2) reacting the compound of the followingFormula 5 with a compound of the following Formula 6 to prepare acompound of the following Formula 1.

in Formulas 1, and 3 to 6, R₁ to R₉ each independently representhydrogen, a silyl, an alkyl having 1 to 20 carbon atoms, an alkenylhaving 2 to 20 carbon atoms, an aryl having 6 to 20 carbon atoms, analkylaryl having 7 to 20 carbon atoms, an arylalkyl having 7 to 20carbon atoms or a metalloid radical of a Group 14 metal substituted witha hydrocarbyl having 1 to 20 carbon atoms; two or more adjacent groupsof the R₁ to R₈ may be connected to each other to form an aliphatic ringhaving 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbonatoms; the aliphatic ring or aromatic ring may be substituted with ahalogen, an alkyl having 1 to 20 carbon atoms, an alkenyl having 2 to 20carbon atoms or an aryl having 6 to 20 carbon atoms; and n is 1 or 2.

Further, in Formulas 1, and 3 to 6, R₁ to R₉ each may independentlyrepresent hydrogen, an alkyl having 1 to 20 carbon atoms, an aryl having6 to 20 carbon atoms, an alkylaryl having 7 to 20 carbon atoms, or anarylalkyl having 7 to 20 carbon atoms; two or more adjacent groups ofthe R₁ to R₈ may be connected to each other to form an aliphatic ringhaving 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbonatoms; and the aliphatic ring or aromatic ring may be substituted with ahalogen, an alkyl having 1 to 20 carbon atoms, or an aryl having 6 to 20carbon atoms.

(1) Step of Reacting Compound of Formula 3 with Compound of Formula 4 toPrepare Compound of Formula 5

In Step (1), a compound of Formula 5 is prepared by reacting a compoundof Formula 3 with a compound of Formula 4.

The reaction of Step (1) may be carried out in the presence of apalladium catalyst under basic conditions, and the reaction may becarried out in an organic solvent such as toluene.

The palladium catalyst may be one or more selected from the groupconsisting of tetrakis(triphenylphosphine) palladium [Pd(PPh₃)₄],palladium chloride (PdCl₂), palladium acetate (Pd(OAc)₂),bis(dibenzylideneacetone) palladium (Pd(dba)₂) and Pd(tBu₃P₂).

A type of a base for forming the basic conditions is not particularlylimited, and specific examples thereof include tBuOLi, tribasicpotassium (K₃PO₄), potassium carbonate (K₂CO₃), cesium carbonate(Cs₂CO₃), potassium fluoride (KF), sodium fluoride (NaF), cesiumfluoride (CsF), tetrabutylammonium fluoride (TBAF) or a mixture thereof.

The reaction of Step (1) may be carried out by a method of reacting in atemperature range of 0 to 140° C., specifically from 40 to 100° C. for 1to 48 hours, specifically 2 to 12 hours.

The compound of Formula 3 and the compound of Formula 4 each may bepreviously added to separate solvents and then mixed again, and apalladium catalyst may be added thereto after mixing. For example, thecompound of Formula 3 may be added to a mixed solvent of water andalcohol such as ethanol, and the compound of Formula 4 may be added to asolvent such as toluene.

Here, the compound of Formula 3 may be prepared by a reactionrepresented by the following Reaction Formula 2.

In Reaction Formula 2, R₆ to R₉ and n are as defined in Formula 3.

A compound of Formula 3-1 is added to an organic solvent such as hexaneand n-BuLi is further added in a temperature range of −80 to 0° C. Here,the n-BuLi may be reacted with a compound of Formula 3-1 in a molarratio of 1:1 to 1:2, and specifically, in a molar ratio of 1:1.1 to1:1.2. After n-BuLi is added, a mixture is reacted at room temperaturefor 1 to 48 hours and filtered, a solvent is added to the obtainedcompound, CO₂ is bubbled into the compound at a temperature of −160 to−20° C., and thereby a compound of Formula 3-2 may be obtained. Acompound of Formula 3-3 may be obtained by adding t-BuLi to the obtainedcompound of Formula 3-2 and performing a reaction in a temperature rangeof −80 to 0° C. After2-isopropyloxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane is added to thecompound of Formula 3-3 at a temperature of −150 to −20° C., thereaction is allowed to proceed by gradually raising the temperature toroom temperature, and thereby a compound of Formula 3 may be obtained.Here, a process of adding HCl and ethyl acetate (EA), washing an organiclayer with NaOH and NaHCO₃, and then dehydration with MgSO₄ may beperformed.

(2) Step of Reacting Compound of Formula 5 with Compound of Formula 6 toPrepare Compound of Formula 1

In Step (2), a compound of Formula 1 is prepared by reacting a compoundof Formula 5 with a compound of Formula 6.

In Step (2), a compound of Formula 5 is reacted with an organolithiumcompound of Formula 6 to introduce R₂ into Formula 5.

In Step (2), the compound of Formula 5 and the compound of Formula 6 maybe reacted in a molar ratio of 1:1 to 1:3, and specifically in a molarratio of 1:1 to 1:2.

The reaction of Step (2) may be carried out by a method of adding thecompound of Formula 6 to the compound of Formula 5 to react in atemperature range of −160 to −20° C., and specifically, may be carriedout by a method of adding the compound of Formula 6 to the compound ofFormula 5 to react in a temperature range of −120 to −40° C. Thereaction may be carried out in an organic solvent such as diethyl ether,and quenched with NH₄Cl or the like when the reaction is completed.

The compound of Formula 1 prepared through Steps (1) and (2) may befurther subjected to Step (3) of recrystallization, and thus the methodof preparing the transition metal compound according to an example ofthe present invention may further include Step (3) of recrystallizingthe compound of Formula 1 after Step (2).

The recrystallization may be performed using an organic solvent such astoluene as a reaction solvent, and purified through recrystallization toobtain a pure compound of Formula 1.

Further, the transition metal compound represented by Formula 2 of thepresent invention may be prepared by a method including the followingsteps: (a) reacting a ligand compound of Formula 1 with an organolithiumcompound to prepare a compound of Formula 7; and (b) reacting a compoundof the following Formula 7 with a compound of the following Formula 8 toprepare a compound of the following Formula 2.

Where in Formulas, R₁ to R₉ each independently represent hydrogen, asilyl, an alkyl having 1 to 20 carbon atoms, an alkenyl having 2 to 20carbon atoms, an aryl having 6 to 20 carbon atoms, an alkylaryl having 7to 20 carbon atoms, an arylalkyl having 7 to 20 carbon atoms or ametalloid radical of a Group 14 metal substituted with a hydrocarbylhaving 1 to 20 carbon atoms; two or more adjacent groups of the R₁ to R₈may be connected to each other to form an aliphatic ring having 5 to 20carbon atoms or an aromatic ring having 6 to 20 carbon atoms; thealiphatic ring or aromatic ring may be substituted with a halogen, analkyl having 1 to 20 carbon atoms, an alkenyl having 2 to 20 carbonatoms or an aryl having 6 to 20 carbon atoms; n is 1 or 2;

Q¹ and Q² each independently represent hydrogen, a halogen, an alkylhaving 1 to 20 carbon atoms, an alkenyl having 2 to 20 carbon atoms, anaryl having 6 to 20 carbon atoms, an alkylaryl having 6 to 20 carbonatoms, an arylalkyl having 7 to 20 carbon atoms, an alkylamido having 1to 20 carbon atoms, an arylamido having 6 to 20 carbon atoms, or analkylidene having 1 to 20 carbon atoms;

X is a halogen; and

M is Ti, Zr or Hf.

Further, R₁ to R₉ each may independently represent hydrogen, an alkylhaving 1 to 20 carbon atoms, an aryl having 6 to 20 carbon atoms, analkylaryl having 7 to 20 carbon atoms, or an arylalkyl having 7 to 20carbon atoms; two or more adjacent groups of R₁ to R₈ may be connectedto each other to form an aliphatic ring having 5 to 20 carbon atoms oran aromatic ring having 6 to 20 carbon atoms; the aliphatic ring oraromatic ring may be substituted with a halogen, an alkyl having 1 to 20carbon atoms, or an aryl having 6 to 20 carbon atoms.

Further, a method of preparing the transition metal compound of thepresent invention may include a step of further reacting a compound ofFormula 2 with a Grignard reagent of the following Formula 9.QMgBr  [Formula 9]

in Formula 9, Q is hydrogen, an alkyl having 1 to 20 carbon atoms, analkenyl having 2 to 20 carbon atoms, an aryl having 6 to 20 carbonatoms, an alkylaryl having 6 to 20 carbon atoms, an arylalkyl having 7to 20 carbon atoms, an alkylamido having 1 to 20 carbon atoms, anarylamido having 6 to 20 carbon atoms, or an alkylidene having 1 to 20carbon atoms.

Here, Q¹, Q² or both of them may be halogens in the compound of Formula2 which reacts with the Grignard reagent of Formula 9. That is, when Q¹,Q², or both of them of Formula 8 are halogens, a compound in which Q¹,Q², or both of them bonded to M in Formula 2 are halogens is prepared.In this case, Q¹, Q², or both of them in Formula 2 may be halogenssubstituted with Q by further reaction with the Grignard reagent ofFormula 9.

(a) Step of Reacting Compound of Formula 1 with Organolithium Compoundto Prepare Compound of Formula 7

In Step (a), a compound of Formula 7 is prepared by reacting a compoundof Formula 1 with an organolithium compound.

In Step (1), the compound of Formula 1 and the organolithium compoundmay be reacted in a molar ratio of 1:1 to 1:3, and specifically in amolar ratio of 1:1 to 1:2.

The reaction of Step (1) may be carried out in an organic solvent suchas diethoxyethane or ether, and may be carried out by adding theorganolithium compound to the compound of Formula 1 in an organicsolvent.

The organolithium compound may be one or more selected from the groupconsisting of n-butyllithium, sec-butyllithium, methyllithium,ethyllithium, isopropyllithium, cyclohexyllithium, allylithium,vinyllithium, phenyllithium and benzyllithium.

The reaction of Step (a) may be carried out by a method of adding theorganolithium compound to the compound of Formula 1 in a temperaturerange of −78 to 0° C. and performing a reaction for 1 to 6 hours,specifically 1 to 4 hours. Here, the reaction temperature may be lessthan 20° C., and specifically, may be in the range of −78 to 0° C.

(b) Step of Reacting Compound of Formula 7 with Compound of Formula 8 toPrepare Compound of Formula 2

In Step (b), a compound of Formula 2 is prepared by reacting a compoundof Formula 7 obtained by Step (a) with a compound of Formula 8.

In Step (b), the compound of Formula 7 and the compound of Formula 8 maybe reacted in a molar ratio of 1:0.8 to 1:1.8, and specifically in amolar ratio of 1:1 to 1:1.2.

The reaction of Step (b) may be carried out by a method of raising thetemperature to a temperature ranging from 40 to 140° C., specifically 70to 120° C., and then performing a reaction for 1 to 48 hours,specifically 1 to 4 hours, and the reaction in Step (a) and Step (b) maybe performed in one step.

That is, the reaction of Step (a) and Step (b) may be performed by amethod of adding the organolithium compound to the compound of Formula 1in a temperature range of −20 to 30° C., further adding the compound ofFormula 8 thereto, raising the temperature to a temperature ranging from40 to 140° C., specifically to a temperature ranging from 70 to 120° C.,and then performing a reaction for 1 to 48 hours, and specifically for 1to 4 hours.

Accordingly, the transition metal compound of Formula 2 may be prepared.

Further, when Q¹, Q² or both of them in the transition metal compound ofFormula 2 are halogens, the additional reaction with the Grignardreagent of Formula 9 may be performed. Here, the reaction between thetransition metal compound of Formula 2 and the Grignard reagent ofFormula 9 may be performed according to the known Grignard reaction.

A transition metal compound prepared by the additional reaction may berepresented by one of the following Formulas 9a to 9c.

More specifically, the transition metal compound according to thepresent invention may be used as a catalyst for the polymerizationreaction alone or in the form of a composition further including one ormore of cocatalyst compounds represented by the following Formulas 10,11 and 12 in addition to the transition metal compound.—[Al(R₇)—O]_(m)—  [Formula 10]

in Formula 10, R₇ may be the same or different from each other and eachindependently represents a halogen, a hydrocarbon having 1 to 20 carbonatoms or a halogen-substituted hydrocarbon having 1 to 20 carbon atoms,and m is an integer of 2 or more;J(R₇)₃  [Formula 11]

in Formula 11, R₇ is as defined in Formula 10, and J is aluminum orboron;[E-H]⁺[ZA₄]⁻ or [E]⁺[ZA₄]⁻  [Formula 12]

in Formula 12, E is a neutral or cationic Lewis base, H is a hydrogenatom, Z is a Group 13 element, and A may be the same or different fromeach other and each independently represents an aryl group having 6 to20 carbon atoms or an alkyl group having 1 to 20 carbon atoms, of whichone or more hydrogen atoms are unsubstituted or substituted with ahalogen, a hydrocarbon having 1 to 20 carbon atoms, alkoxy, or phenoxy.

Examples of the compound represented by Formula 10 include methylaluminoxane, ethyl aluminoxane, isobutyl aluminoxane, and butylaluminoxane, and a more preferable compound is methyl aluminoxane.

Examples of the compound represented by Formula 11 include trimethylaluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum,tributyl aluminum, dimethylchloroaluminum, triisopropyl aluminum,tri-s-butyl aluminum, tricyclopentyl aluminum, tripentyl aluminum,triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyldimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum,tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminumethoxide, trimethylboron, triethylboron, triisobutylboron,tripropylboron, tributylboron and the like, and a more preferablecompound is selected from trimethyl aluminum, triethyl aluminum andtriisobutyl aluminum.

Examples of the compound represented by Formula 12 includetriethylammonium tetraphenylboron, tributylammonium tetraphenylboron,trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron,trimethylammonium tetra(p-tolyl) boron, trimethylammoniumtetra(o,p-dimethylphenyl) boron, tributylammoniumtetra(p-trifluoromethylphenyl) boron, trimethylammoniumtetra(p-trifluoromethylphenyl) boron, tributylammoniumtetrapentafluorophenylboron, N,N-diethylanilinium tetraphenylboron,N,N-diethylanilinium tetrapentafluorophenylboron, diethylammoniumtetrapentafluorophenylboron, triphenylphosphonium tetraphenylboron,trimethylphosphonium tetraphenylboron, dimethylaniliniumtetrakis(pentafluorophenyl) borate, triethylammonium tetraphenylaluminum, tributylammonium tetraphenyl aluminum, trimethylammoniumtetraphenyl aluminum, tripropylammonium tetraphenyl aluminum,trimethylammonium tetra(p-tolyl) aluminum, tripropylammoniumtetra(p-tolyl) aluminum, triethylammonium tetra(o,p-dimethylphenyl)aluminum, tributylammonium tetra(p-trifluoromethylphenyl) aluminum,trimethylammonium tetra(p-trifluoromethylphenyl) aluminum,tributylammonium tetrapentafluorophenyl aluminum, N,N-diethylaniliniumtetraphenyl aluminum, N,N-diethylanilinium tetrapentafluorophenylaluminum, diethylammonium tetrapentatetraphenyl aluminum,triphenylphosphonium tetraphenyl aluminum, trimethylphosphoniumtetraphenyl aluminum, tripropylammonium tetra(p-tolyl) boron,triethylammoniumtetra(o,p-dimethylphenyl) boron, triphenylcarboniumtetra(p-trifluoromethylphenyl) boron, triphenylcarboniumtetrapentafluorophenylboron, etc.

Specifically, aluminoxane may be used, and more specifically,methylaluminoxane (MAO) which is an alkylaluminoxane may be used.

As the first method, the catalyst composition may be prepared using amethod including the following steps: 1) contacting the transition metalcompound represented by Formula 2 with the compound represented byFormula 10 or 11 to obtain a mixture; and 2) adding the compoundrepresented by Formula 12 to the mixture.

Further, as the second method, the catalyst composition may be preparedusing a method of contacting the transition metal compound representedby Formula 2 with the compound represented by Formula 10.

In the first method among the methods of preparing the catalystcomposition, the molar ratio of the transition metal compoundrepresented by Formula 2/the compound represented by Formula 10 or 11may preferably be 1/5,000 to ½, may more preferably be 1/1,000 to 1/10,and more specifically 1/500 to 1/20. When the molar ratio of thetransition metal compound represented by Formula 2/the compoundrepresented by Formula 10 or 11 exceeds ½, the amount of an alkylatingagent is very small, and the alkylation of a metal compound may not becompletely carried out, and when the molar ratio is less than 1/5,000,the activation of the alkylated metal compound may not be completelycarried out due to the side reaction of the remaining excessivealkylating agent with the activation agent which is the compound ofFormula 12 even though the alkylation of the metal compound may becarried out. Further, the molar ratio of the transition metal compoundrepresented by Formula 2/the compound represented by Formula 12 maypreferably be 1/25 to 1, may more preferably be 1/10 to 1, and morespecifically ⅕ to 1. When the molar ratio of the transition metalcompound represented by Formula 2/the compound represented by Formula 12exceeds 1, the amount of the activation agent is relatively small, andthe activation of the metal compound may not be completely carried out,thereby deteriorating the activity of the catalyst composition prepared.When the molar ratio is less than 1/25, the remaining excessive amountof the activation agent may decrease the economic performance in termsof the unit price of the catalyst composition, or the purity of apolymer thus produced may be decreased even though the activation of themetal compound may be completely carried out.

In the second method among the methods of preparing the catalystcomposition, the molar ratio of the transition metal compoundrepresented by Formula 2/the compound represented by Formula 10 maypreferably be 1/10,000 to 1/10, may more preferably be 1/5,000 to 1/100,and more specifically 1/3,000 to 1/500. When the molar ratio exceeds1/10, the amount of the activation agent is relatively small, and theactivation of the metal compound may not be completely carried out,thereby deteriorating the activity of the catalyst composition prepared.When the molar ratio is less than 1/10,000, the remaining excessiveamount of the activation agent may decrease the economic performance interms of the unit price of the catalyst composition, or the purity of apolymer thus produced may be decreased even though the activation of themetal compound may be completely carried out.

Further, in an example of the present invention, when the transitionmetal compound according to the present invention is used as a catalystfor the polymerization reaction, it may be used as a catalyst for thepolymerization reaction in the form of a composition further including achain shuttling agent.

The chain shuttling agent refers to a compound allowing an exchange ofpolymeric chains (i.e., polymer chains or fragments) between two or moreactive catalyst sites of two olefin polymerization catalysts underolefin polymerization conditions, and the two olefin polymerizationcatalysts may be the transition metal compounds of the presentinvention. That is, the transfer of the polymer fragments occurs in oneor more of the active sites of the transition metal compound.

Examples of the chain shuttling agent include trialkyl aluminum anddialkyl zinc compounds, especially triethyl aluminum, tri(i-propyl)aluminum, tri(i-butyl) aluminum, tri(n-hexyl) aluminum, tri(n-octyl)aluminum, triethyl gallium or diethyl zinc, and organometalliccompounds, specifically tri((C₁-C₈)alkyl) aluminum or di((C₁-C₈)alkyl)zinc compounds, especially triethyl aluminum, tri(i-propyl) aluminum,tri(i-butyl) aluminum, tri(n-hexyl) aluminum, tri(n-octyl) aluminum, ora reaction product or mixture formed by a combination of diethyl zincand a primary or secondary amine, a primary or secondary phosphine, athiol, or a hydroxyl compound, especially bis (trimethylsilyl) amine,t-butyl (dimethyl) silanol, 2-hydroxymethylpyridine, di(n-pentyl) amine,2,6-di(t-butyl) phenol, ethyl (1-naphthyl) amine,bis(2,3,6,7-dibenzo-1-azacycloheptanamine), diphenylphosphine,2,6-di(t-butyl) thiophenol or 2,6-diphenylphenol in an amount less thana stoichiometric amount (with respect to number of hydrocarbyl groups).Preferably, a sufficient amine, phosphine, thiol or hydroxyl reagent isused such that at least one hydrocarbyl group per metal atom remains.The main reaction product of the most preferable combination for use inthe present invention as a shuttling agent includes n-octyl aluminumdi(bis(trimethylsilyl) amide), i-propyl aluminum bis(dimethyl(t-butyl)siloxide), and n-octyl aluminum di(pyridinyl-2-methoxide), i-butylaluminum bis(dimethyl(t-butyl) siloxane), i-butyl aluminumdi(bis(trimethylsilyl) amide), n-octyl aluminumdi(pyridine-2-methoxide), i-butyl aluminum bis(di(n-pentyl) amide),n-octyl aluminum bis(2,6-di-t-butylphenoxide), n-octyl aluminumdi(ethyl(1-naphthyl) amide), ethyl aluminum bis(t-butyl dimethylsiloxide), ethyl aluminum di(bis(trimethylsilyl) amide), ethyl aluminumbis(2,3,6,7-dibenzo-1-azacycloheptanamide), n-octyl aluminumbis(2,3,6,7-dibenzo-1-azacycloheptanamide), n-octyl aluminumbis(dimethyl (t-butyl) siloxide, ethyl zinc (2,6-diphenylphenoxide), andethyl zinc (t-butoxide).

Hydrocarbon-based solvents such as pentane, hexane, heptane and thelike, or aromatic solvents such as benzene, toluene and the like may beused as the reaction solvent in the preparation of the catalystcomposition.

Further, the catalyst composition may include the transition metalcompound and a cocatalyst compound in the form of being supported on acarrier.

Specifically, the polymerization reaction for polymerizing anolefin-based monomer in the presence of a catalyst compositioncontaining the transition metal compound may be carried out by asolution polymerization process, a slurry process or a gas phase processusing a continuous-slurry polymerization reactor, a loop slurry reactor,a gas phase reactor or a solution reactor. Further, homopolymerizationwith one olefin monomer or copolymerization with two or more types ofmonomers may be performed.

The polymerization of the polyolefin may be carried out by reaction at atemperature of about 25 to about 500° C. and a pressure of about 1 toabout 100 kgf/cm².

Specifically, the polymerization of the polyolefin may be carried out ata temperature of about 25 to about 500° C., specifically about 25 to200° C., and more specifically about 50 to 100° C. Further, a reactionpressure may be about 1 to about 100 kgf/cm², specifically about 1 toabout 50 kgf/cm², and more specifically about 5 to about 40 kgf/cm².

Further, examples of olefinic monomers polymerizable using thetransition metal compound and cocatalyst according to an embodiment ofthe present invention include ethylene, alpha-olefins, cyclic olefinsand the like, and diene olefin-based monomers or triene olefin-basedmonomers having two or more double bonds may also be polymerized.

In the polyolefin prepared according to the present invention, specificexamples of the olefin-based monomer include ethylene, propylene,1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene,1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene,1-eicosene and the like, or a copolymer obtained by copolymerizing twoor more thereof.

The polyolefin may be, but is not limited to, a propylene polymer.

The polymer may be either a homopolymer or a copolymer. When the olefinpolymer is a copolymer of ethylene and another comonomer, the monomerforming the copolymer is preferably ethylene, and at least one comonomerselected from the group consisting of propylene, 1-butene, 1-hexene, and4-methyl-1-pentene and 1-octene.

MODES OF THE INVENTION

Hereinafter, preferred examples are provided to allow for a clearerunderstanding of the present invention. However, the following examplesare merely presented to exemplify the present invention, and the scopeof the present invention is not limited thereto.

Synthesis of Ligand and Transition Metal Compound

Organic reagents and solvents were purchased from Aldrich and Merck, andpurified by a standard method and used. In all synthetic steps, thecontact of the air and moisture were blocked to improve thereproducibility of experiments. Spectrums and images were obtained byusing 500 MHZ nuclear magnetic resonance (NMR) for the identification ofthe structure of the compound.

EXAMPLES Example 1: Synthesis of Ligand Compound a) Preparation of8-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,2,3,4-tetrahydroquinoline

THQ (6 g, 45.05 mmol, 1 eq) was added to a Schlenk flask andvacuum-dried, hexane (150 mL, 0.3 M) was added thereto, and n-BuLi(19.82 mL, 49.56 mmol, 1.1 eq, 2.5 M in hexane) was added thereto at−20° C. The mixture was reacted overnight at room temperature andfiltered to obtain a lithium compound. Diethyl ether (53.9 mL, 0.4 M)was added to the lithium compound (3 g, 21.56 mmol, 1 eq) thus obtainedand bubbled with CO₂ at −78° C. After the mixture was left at roomtemperature overnight, THF (1.1 eq, 1.71 g, 23.72 mmol) was added at−20° C. t-BuLi (13.95 mL, 23.72 mmol, 1.1 eq, 1.7 M) was added theretoand reacted at −20° C. for 2 hours, and then2-isopropyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (10.03 g, 53.9 mmol,2.5 eq) was added at −78° C. The temperature was gradually raised toroom temperature, and a 1M HCl aqueous solution and EA were added at 0°C. after the reaction was complete. An organic layer was washed with 1 MNaOH and 1M NaHCO₃, and dehydrated with MgSO₄. 1.4 g of a yellow oilyproduct was obtained in a yield of 25%.

¹H-NMR (CDCl₃): 7.42 (d, 1H), 6.97 (d, 1H), 6.48 (t, 1H), 5.70 (s, 1H),3.34 (m, 2H), 2.73 (t, 2H), 1.90 (m, 2H), 1.31 (s, 12H)

b) Preparation of N-(2,6-diisopropylphenyl)-1-(6-bromopyridin-2-yl)Methanimine

p-toluenesulfonic acid (3 drops) and a molecular sieve (1 g) were addedto 2-formyl-6-bromopyridine (9.22 g, 49.57 mmol, 1 eq), and then toluene(100 mL) was added thereto. 2,6-diisopropylaniline (9.66 g, 54.52 mmol,1.1 eq) was added thereto, stirred at 70° C. for 12 hours, and thencooled to room temperature. The molecular sieve was filtered, thesolvent was removed and vacuum-drying was performed to produce a solid.MeOH was added at 50° C. under heating and then cooled to roomtemperature to obtain a solid. The resulting product was firstlyfiltered to obtain a solid, and then secondarily recrystallized in arefrigerator to obtain a secondary solid. Accordingly, 15.5 g of a solidwas obtained in a yield of 90.5%.

c) Preparation ofN-(2,6-diisopropylphenyl)-1-(6-(1,2,3,4-tetrahydroquinolin-8-yl)pyridin-2-yl) Methanimine

The N-(2,6-diisopropylphenyl)-1-(6-bromopyridin-2-yl) methanimine (1.799g, 5.209 mmol, 1 eq) prepared as above was added to toluene (8 mL) andstirred. Meanwhile, separately, Na₂CO₃ (1.380 g, 13.0225 mmol, 2.5 eq)and tetrahydroquinoline-borolane (THQ-borolane) (1.350 g, 5.209 mmol, 1eq) were added to a solvent including H₂O (1.6 mL) and EtOH (1.6 mL) ina ratio of 1:1 and stirred.

A Br-imine toluene solution was transferred to the solution of Na₂CO₃and THQ-borolane, followed by the addition of Pd(PPh₃)₄ (0.018 g, 0.0156mmol, 0.3 mol % Pd). The mixture was stirred at 70° C. for 4 hours andcooled to room temperature. An organic layer was extracted withtoluene/brine and dehydrated with Na₂SO₄ (product: 0.98 g, yield: 47%).

¹H-NMR (toluene_d8): 8.88 (s, 1H), 8.38 (s, 1H), 7.92 (d, 1H), 7.33 (d,2H), 7.20 (t, 1H), 7.18 (t, 2H), 6.91 (d, 1H), 6.63 (t, 1H), 3.20 (m,4H), 2.62 (m, 2H), 1.63 (m, 2H), 1.20 (d, 12H)

d) Preparation of(2,6-diisopropylphenyl)-N-(phenyl(6-(1,2,3,4-tetrahydroquinolin-8-yl)pyridin-2-yl)methyl) Aniline

N-(2,6-diisopropylphenyl)-1-(6-(1,2,3,4-tetrahydroquinolin-8-yl)pyridin-2-yl)methanimine (0.95 g, 2.39 mmol, 1 eq) prepared as above was dissolved indiethyl ether (23.9 mL), the temperature was lowered to −78° C., andthen phenyllithium (3.583 mL, 6.45 mmol, 2.7 eq, 1.8 M in DBE) was addedthereto. When the reaction was complete, the mixture was quenched with 1N NH₄Cl and worked up with diethyl ether and water. Accordingly, 1.2 g(quantitative yield) of an orange solid was obtained.

¹H-NMR (toluene_d8): 8.01 (s, 1H), 7.41 (d, 2H), 7.31 (d, 1H), 7.15 (m,4H), 7.06 (m, 3H), 6.86 (d, 2H), 6.73 (t, 1H), 6.61 (t, 1H), 5.24 (d,1H), 4.32 (d, 1H), 3.05 (m, 2H), 3.0 (m, 2H), 2.52 (m, 2H), 1.52 (m,2H), 1.01 (m, 12H)

Example 1-1: Synthesis of Transition Metal Compound (Formula 2a)

2,6-diisopropylphenyl-N-(phenyl(6-(1,2,3,4-tetrahydroquinolin-8-yl)pyridin-2-yl)methyl) aniline (0.8 g, 1.682 mmol, 1 eq) prepared in d) of Example 1was added to toluene (5.607 mL, 0.3 M) and stirred, and then n-BuLi(1.413 mL, 3.532 mmol, 2.1 eq) was added dropwise thereinto. HfCl₄(0.566 g, 1.766 mmol, 1.0 eq) was added and the mixture was heated at 90to 100° C. for 2 hours. After the reaction was complete, the reactionmixture was cooled to room temperature, and MeMgBr (1.962 mL, 5.887mmol, 3.5 eq, 3.0 M in DEE) was added, and the mixture was allowed toreact at room temperature overnight. The solvent was vacuum-dried andthen filtered. 588 mg of a yellow solid was obtained in a yield of51.2%.

¹H-NMR (toluene_d8): 7.29 (d, 1H), 7.20 (d, 1H), 7.12 (m, 1H), 7.11 (m,2H), 7.05 (m, 6H), 6.89 (t, 1H), 6.67 (t, 1H), 6.51 (d, 1H), 5.93 (s,1H), 4.38 (d, 1H), 3.89 (t, 1H), 3.49 (t, 1H), 3.11 (m, 1H), 2.86 (m,1H), 2.63 (m, 1H), 1.95 (m, 2H), 1.43 (d, 3H), 1.23 (d, 3H), 1.01 (d,3H), 0.56 (s, 3H), 0.46 (d, 3H), 0.00 (s, 3H)

Example 1-2: Synthesis of Transition Metal Compound (Formula 2b)

2,6-diisopropylphenyl-N-(phenyl(6-(1,2,3,4-tetrahydroquinolin-8-yl)pyridin-2-yl)methyl) aniline (0.82 g, 1.724 mmol, 1 eq) prepared in d) of Example 1was added to toluene (5.747 mL, 0.3 M) and stirred, and then n-BuLi(1.45 mL, 3.6204 mmol, 2.1 eq) was added dropwise thereinto. ZrCl₄(0.422 g, 1.810 mmol, 1.05 eq) was added and the mixture was heated at90 to 100° C. for 2 hours.

After the reaction was complete, the reaction mixture was cooled to roomtemperature and MeMgBr (2.011 mL, 6.034 mmol, 3.5 eq, 3.0M in DEE) wasadded and allowed to react at room temperature overnight. The solventwas vacuum-dried and then filtered. The celite-filtered filtrate wasdried, hexane was added thereto, the mixture was stirred andvacuum-dried, pentane was further added thereto, and the mixture wasstirred and vacuum-dried. When a solid was obtained, pentane was addedthereto to precipitate a catalyst. 672 mg of an orange solid wasobtained in a yield of 65.5%.

¹H-NMR (toluene_d8): 7.30 (d, 1H), 7.20 (d, 1H), 7.12 (m, 2H), 7.06 (m,7H), 6.89 (t, 1H), 6.67 (t, 1H), 6.54 (d, 1H), 5.73 (s, 1H), 4.80 (d,1H), 3.99 (m, 1H), 3.57 (t, 1H), 3.07 (m, 1H), 2.86 (m, 1H), 2.67 (m,1H), 1.95 (m, 2H), 1.45 (d, 3H), 1.21 (d, 3H), 0.96 (d, 3H), 0.68 (s,3H), 0.50 (d, 3H), 0.09 (s, 3H)

Example 2: Synthesis of Ligand Compound Synthesis of2,6-diisopropyl-N-((2-isopropylphenyl)(6-(1,2,3,4-tetrahydroquinolin-8-yl)pyridin-2-yl) methyl) Aniline

1-Br-2-isopropylbenzene (2.13 g, 10.67 mmol, 2.7 eq) was added to THF(21.38 mL) and t-BuLi (13.62 mL) was added at −78° C. The reaction wasallowed to proceed for 2 hours and then the reaction product was warmedto room temperature.

Diethyl ether was added toN-(2,6-diisopropylphenyl)-1-(6-(1,2,3,4-tetrahydroquinolin-8-yl)pyridin-2-yl) methanimine, and cumene lithium was added dropwise at −78°C. After the temperature was raised to room temperature, the reactionwas performed overnight, the reaction product was quenched with 1N NH₄Cland ether/H₂O work-up was carried out. Dehydration was performed usingNa₂SO₄ and the solvent was vacuum-dried with a rotavapor. 2.22 g of pureyellow oil was obtained in a quantitative yield.

¹H-NMR (toluene_d8): 7.97 (s, 1H), 7.66 (d, 1H), 7.30 (d, 1H), 7.14 (m,8H), 6.83 (d, 1H), 6.56 (t, 1H), 5.61 (d, 1H), 4.04 (d, 1H), 2.9 (m,5H), 2.5 (m, 2H), 1.51 (m, 2H), 1.01 (d, 12H), 1.00 (d, 3H), 0.97 (d,3H)

Example 2-1: Synthesis of Transition Metal Compound (Formula 2c)

2,6-diisopropyl-N-((2-isopropylphenyl)(6-(1,2,3,4-tetrahydroquinolin-8-yl)pyridin-2-yl) methyl) aniline (1 g, 1.9314 mmol, 1 eq) obtained inExample 2 was added to toluene (6.433 mL, 0.3 M) and stirred, and n-BuLi(1.622 mL, 4.056 mmol, 2.1 eq) was added dropwise. HfCl₄ (0.619 g,1.9314 mmol, 1.0 eq) was added and the mixture was heated at 90 to 100°C. for 2 hours. After the reaction was complete, the reaction mixturewas cooled, MeMgBr (2.2533 mL, 6.76 mmol, 3.5 eq, 3.0 M in DEE) wasadded thereto, and the reaction was allowed to proceed overnight at roomtemperature. The solvent was vacuum-dried and then filtered. 680 mg of ayellow solid was obtained in a yield of 33%.

¹H-NMR (toluene_d8): 7.29 (m, 2H), 7.21 (d, 1H), 7.10 (m, 6H), 6.88 (t,1H), 6.89 (t, 1H), 6.68 (t, 1H), 6.60 (d, 1H), 6.55 (s, 1H), 4.42 (d,1H), 3.93 (m, 1H), 3.49 (t, 1H), 3.19 (m, 1H), 2.82 (m, 2H), 2.67 (m,1H), 1.97 (m, 2H), 1.41 (d, 3H), 1.18 (m, 6H), 1.01 (d, 3H), 0.70 (d,3H), 0.60 (s, 3H), 0.45 (d, 3H), 0.03 (s, 3H)

Example 2-2: Synthesis of Transition Metal Compound (Formula 2d)

2,6-diisopropyl-N-((2-isopropylphenyl)(6-(1,2,3,4-tetrahydroquinolin-8-yl)pyridin-2-yl) methyl) aniline (1.32 g, 2.5494 mmol, 1 eq) obtained inExample 2 was added to toluene (8.5 mL, 0.3 M) and stirred, and n-BuLi(2.1415 mL, 5.354 mmol, 2.1 eq) was added dropwise. ZrCl₄ (0.594 g,2.5494 mmol, 1.05 eq) was added and the mixture was heated at 90 to 100°C. for 2 hours.

After the reaction was complete, the reaction mixture was cooled, MeMgBr(2.974 mL, 8.923 mmol, 3.5 eq, 3.0 M in DEE) was added thereto, and thereaction was allowed to proceed overnight at room temperature. Thesolvent was vacuum-dried and then filtered. The celite-filtered filtratewas dried, hexane was added thereto, the mixture was stirred andvacuum-dried, pentane was further added thereto, and the mixture wasstirred and vacuum-dried. When a solid was obtained, pentane was addedthereto to precipitate a catalyst. 310 mg of an orange solid wasobtained in a yield of 20%.

¹H-NMR (toluene_d8): 7.26 (m, 2H), 7.23 (d, 1H), 7.10 (m, 6H), 7.02 (m,1H), 6.87 (t, 1H), 6.69 (t, 1H), 6.64 (d, 1H), 6.36 (s, 1H), 4.85 (d,1H), 4.03 (m, 1H), 3.56 (t, 1H), 3.15 (m, 1H), 2.85 (m, 2H), 2.67 (m,1H), 1.97 (m, 2H), 1.42 (d, 3H), 1.17 (m, 6H), 0.94 (d, 3H), 0.71 (m,6H), 0.49 (d, 3H), 0.12 (d, 3H)

Example 3: Synthesis of Ligand Compound a) Synthesis ofmethyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) Indolin

After 2-methylindoline (10 g, 75.08 mmol, 1 eq) was dissolved in hexane(250 mL, 0.3 M) followed by lithiation by adding n-BuLi (33.03 mL, 82.59mol, 1.1 eq), the reaction was performed overnight, and the mixture wasfiltered to obtain a solid.

Diethyl ether (99.2 mL, 0.4 M) was added to the lithium compound (5.52g, 39.675 mmol, 1 eq) thus obtained and bubbled with CO₂ at −78° C. Themixture was stirred at room temperature for 1 day, and THF (1.1 eq, 3.54mL, 43.643 mmol, 1.1 eq) was added at −20° C.

t-BuLi (27.8 mL, 43.643 mmol, 1.1 eq, 1.57 M) was added thereto andreacted at −20° C. for 2 hours, and then2-isopropyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (20.24 g, 99.19mmol, 2.5 eq) was added at −78° C. The temperature was gradually raisedto room temperature, and a 1M HCl aqueous solution and EA were added at0° C. after the reaction was complete. An organic layer was washed with1 M NaOH and 1M NaHCO₃, and dehydrated with MgSO₄. Accordingly, 3.1 g ofa beige solid was obtained in a yield of 30%.

¹H-NMR (CDCl₃): 7.36 (d, 1H), 7.08 (d, 1H), 6.58 (t, 1H), 4.93 (s, 1H),4.01 (m, 1H), 3.07 (m, 1H), 2.60 (m, 1H), 1.31 (s, 12H), 1.25 (s, 3H)

b) Preparation of N-(2,6-diisopropylphenyl)-1-(6-(2-methylindolin-7-yl)pyridin-2-yl) Methanimine

N-(2,6-diisopropylphenyl)-1-(6-bromopyridin-2-yl) methanimine (3 g, 8.69mmol, 1 eq) prepared as above was added to toluene (13.33 mL) andstirred. Meanwhile, separately, Na₂CO₃ (2.303 g, 21.725 mmol, 2.5 eq)and 2 M 2-methyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) indolin(I-borolane) (2.25 g, 8.69 mmol, 1 eq) were added to a solvent includingH₂O (2.66 mL) and EtOH (2.66 mL) in a ratio of 1:1 and stirred.

A Br-imine toluene solution was transferred to the solution ofI-borolane, followed by the addition of Pd(PPh₃)₄ (0.0301 g, 0.026 mmol,0.3 mol % Pd). The mixture was stirred at 70° C. for 4 hours and cooledto room temperature. An organic layer was extracted with toluene/brineand dehydrated with Na₂SO₄. 1.78 g of the product was obtained in ayield of 52%.

¹H-NMR (toluene_d8): 8.38 (s, 1H), 7.86 (d, 1H), 7.66 (s, 1H), 7.38 (d,2H), 7.19 (t, 1H), 7.13 (m, 3H), 6.68 (t, 1H), 3.89 (m, 1H), 3.15 (m,2H), 2.89 (m, 1H), 2.40 (m, 1H), 1.18 (m, 12H), 1.1 (m, 3H)

c) Preparation of 2,6-diisopropyl-N-((6-(2-methylindolin-7-yl)pyridin-2-yl) (phenyl) methyl) Aniline

In order to attach a phenyl to a ligand precursor, the synthesizedligand precursor (750 mg, 1.886 mmol, 1 eq) was dissolved in diethylether (18.86 mL) and the temperature was lowered to −78° C. Then, phenyllithium (2.83 mL, 5.093 mmol, 2.7 eq, 1.8 M in DBE) was added. When thereaction was complete, the mixture was quenched with 1 N NH₄Cl andworked up with diethyl ether and water. Accordingly, 880 mg(quantitative yield) of the ligand was obtained.

¹H-NMR (toluene_d8): 7.40 (m, 3H), 7.24 (d, 1H), 7.14 (m, 3H), 7.06 (m,4H), 6.92 (m, 2H), 6.74 (d, 1H), 6.65 (m, 1H), 5.26 (m, 1H), 4.34 (m,1H), 3.74 (m, 1H), 3.05 (m, 2H), 2.83 (m, 1H), 2.35 (m, 1H), 1.02 (m,12H), 0.93 (m, 3H)

Example 3-1: Synthesis of Transition Metal Compound (Formula 2e)

2,6-diisopropyl-N-((6-(2-methylindolin-7-yl) pyridin-2-yl) (phenyl)methyl) aniline (0.7 g, 1.4716 mmol, 1 eq) which was the ligandsynthesized in d) of Example 3 was added to toluene (4.905 mL, 0.3 M)and stirred, and then n-BuLi (1.236 mL, 3.09 mmol, 2.1 eq) was addeddropwise thereinto. HfCl₄ (0.495 g, 1.5452 mmol, 1.05 eq) was added andthe mixture was heated at 90 to 100° C. for 2 hours. After the reactionwas complete, the reaction mixture was cooled to room temperature andMeMgBr (1.72 mL, 5.1506 mmol, 3.5 eq, 3.0 M in DEE) was added and themixture was allowed to react at room temperature overnight. The solventwas vacuum-dried and then filtered. The celite-filtered filtrate wasdried, hexane was added thereto, the mixture was stirred andvacuum-dried, pentane was further added thereto, and the mixture wasstirred and vacuum-dried. When a solid was obtained, pentane was addedthereto to precipitate to obtain 492 mg of a yellow solid as a catalystwhich is the title compound in a yield of 49%.

¹H-NMR (toluene_d8): 7.40 (d, 1H), 7.30 (d, 1H), 7.17 (d, 2H), 7.04 (m,6H), 6.91 (t, 2H), 6.67 (t, 1H), 6.45 (d, 1H), 5.72 (s, 1H), 4.99 (m,1H), 3.83 (m, 1H), 3.26 (m, 1H), 3.03 (m, 1H), 2.50 (d, 1H), 1.44 (d,3H), 1.32 (d, 3H), 1.17 (d, 3H), 0.95 (d, 3H), 0.70 (s, 3H), 0.49 (d,3H), 0.16 (s, 3H)

Example 4: Synthesis of Ligand Compound Preparation of2,6-diisopropyl-N-((2-isopropylphenyl)(6-(2-methylindolin-7-yl)pyridin-2-yl)methyl) Aniline

THF (13.58 mL) was added to 1-Br-2-isopropylbenzene (1.352 g, 6.79 mmol,2.7 eq), and t-BuLi (8.65 mL) was added at −78° C. The mixture wasreacted for 2 hours and the temperature was raised to room temperature.Diethyl ether (25.15 mL) was added to a ligand precursor (1 g, 2.515mmol, 1 eq), and cumene lithium was added dropwise at −78° C. Thetemperature was raised to room temperature, the reaction was allowed toproceed overnight, the mixture was quenched with 1 N NH₄Cl, and thenworked up with ether/H₂O. Dehydration was performed using Na₂SO₄ and thesolvent was vacuum-dried using a rotavapor. 1.49 g of yellow oil wasobtained in a quantitative yield.

¹H-NMR (toluene_d8): 7.75-5.60 (m, 15H), 4.08-2.30 (m, 7H), 1.13-1.02(m, 21H)

Example 4-1: Synthesis of Transition Metal Compound (Formula 2g)

2,6-diisopropyl-N-((2-isopropylphenyl)(6-(2-methylindolin-7-yl)pyridin-2-yl)methyl) aniline (1.17 g, 2.26 mmol, 1 eq) which was the ligandsynthesized in Example 4 was added to toluene (7.533 mL, 0.3 M) andstirred, and n-BuLi (1.898 mL, 4.745 mmol, 2.1 eq) was added dropwise.HfCl₄ (0.724 g, 2.26 mmol, 1.05 eq) was added and the mixture was heatedat 90 to 100° C. for 2 hours. After the reaction was complete, thereaction mixture was cooled to room temperature and MeMgBr (2.637 mL,7.91 mmol, 3.5 eq, 3.0 M in DEE) was added and allowed to react at roomtemperature overnight. The celite-filtered filtrate was dried, hexanewas added thereto, the mixture was stirred and vacuum-dried, pentane wasfurther added thereto, and the mixture was stirred and vacuum-dried.When a solid was obtained, pentane was added thereto to precipitate toobtain 400 mg of a yellow solid in a yield of 25%.

¹H-NMR (toluene_d8): 7.37 (d, 1H), 7.28 (d, 2H), 7.18 (d, 1H), 7.10 (m,5H), 6.89 (t, 1H), 6.67 (t, 1H), 6.59 (d, 1H), 6.42 (s, 1H), 5.01 (m,1H), 3.92 (m, 1H), 3.26 (m, 1H), 3.10 (m, 1H), 2.84 (m, 1H), 2.52 (d,1H), 1.40 (d, 3H), 1.34 (d, 3H), 1.16 (dd, 6H), 0.95 (d, 3H), 0.74 (s,3H), 0.68 (d, 3H), 0.45 (d, 3H), 0.20 (s, 3H)

Example 5: Synthesis of Ligand Compound a) Preparation of2-methyl-8-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,2,3,4-tetrahydroquinoline

2-methyl-THQ (10 g, 67.925 mmol, 1 eq) was added to a Schlenk flask andvacuum-dried, hexane (226 mL, 0.3 M) was added thereto, and n-BuLi(29.89 mL, 74.718 mmol, 1.1 eq, 2.5 M in hexane) was added thereto at−20° C. The mixture was reacted overnight at room temperature andfiltered to obtain a lithium compound. Diethyl ether (113.21 mL, 0.4 M)was added to the lithium compound (10.40 g, 67.925 mmol, 1 eq) thusobtained and bubbled with CO₂ at −78° C. After the mixture was left atroom temperature overnight, THF (1.1 eq, 5.388 g, 74.72 mmol) was addedat −20° C. t-BuLi (47.6 mL, 74.72 mmol, 1.1 eq, 1.7 M) was addedthereto, and reacted at −20° C. for 2 hours, and then2-isopropyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (31.6 g, 169.8 mmol,2.5 eq) was added at −78° C. The temperature was gradually raised toroom temperature, and a 1M HCl aqueous solution and EA were added at 0°C. after the reaction was complete. An organic layer was washed with 1 MNaOH and 1M NaHCO₃, and dehydrated with MgSO₄. 9.9 g of a yellow oilyproduct was obtained in a yield of 53.4%.

¹H-NMR (CDCl₃): 7.45 (d, 1H), 7.01 (d, 1H), 6.52 (t, 1H), 5.83 (s, 1H),3.48 (m, 1H), 2.80 (m, 2H), 1.91 (m, 1H), 1.58 (m, 1H), 1.35 (s, 12H),1.26 (s, 3H)

b) Preparation ofN-(2,6-diisopropylphenyl)-1-(6-(2-methyl-1,2,3,4-tetrahydroquinolin-8-yl)pyridin-2-yl)Methanimine

The N-(2,6-diisopropylphenyl)-1-(6-bromopyridin-2-yl) methanimine (3 g,8.69 mmol, 1 eq) prepared as above was added to toluene (13.33 mL) andstirred. Meanwhile, separately, Na₂CO₃ (2.303 g, 21.725 mmol, 2.5 eq)and THQ-borolane (2.373 g, 8.69 mmol, 1 eq) were added to a solventincluding H₂O (2.66 mL) and EtOH (2.66 mL) in a ratio of 1:1 andstirred.

A Br-imine toluene solution was transferred to the solution ofTHQ-borolane, followed by the addition of Pd(PPh₃)₄ (0.0301 g, 0.026mmol, 0.3 mol % Pd). The mixture was stirred at 70° C. for 4 hours andcooled to room temperature. An organic layer was extracted withtoluene/brine and dehydrated with Na₂SO₄. 3.08 g of a product wasobtained in a yield of 86%.

¹H-NMR (toluene_d8): 8.96 (s, 1H), 8.41 (s, 1H), 7.92 (d, 1H), 7.33 (d,2H), 7.19 (t, 1H), 7.13 (m, 3H), 6.94 (d, 1H), 6.64 (m, 1H), 3.30 (m,1H), 3.16 (m, 2H), 2.72 (m, 1H), 2.61 (m, 1H), 1.56 (m, 1H), 1.36 (m,1H), 1.19 (m, 12H), 1.05 (d, 3H)

c) Preparation of2,6-diisopropyl-N-((6-(2-methyl-1,2,3,4-tetrahydroquinolin-8-yl)pyridin-2-yl)(phenyl)methyl) Aniline

N-(2,6-diisopropylphenyl)-1-(6-(2-methyl-1,2,3,4-tetrahydroquinolin-8-yl)pyridin-2-yl)methanimine (1 g, 2.43 mmol, 1 eq) which was the synthesized ligandprecursor was dissolved in diethyl ether (24.3 mL), the temperature waslowered to −78° C., and then phenyl lithium (3.645 mL, 6.561 mmol, 2.7eq, 1.8 M in DBE) was added thereto. When the reaction was complete, themixture was quenched with 1 N NH₄Cl and worked up with diethyl ether andwater. Accordingly, 1.2 g (quantitative yield) of the product wasobtained.

¹H-NMR (toluene_d8): 8.20 (s, 1H), 7.33-6.64 (m, 14H), 5.25 (m, 1H),4.51 (m, 1H), 3.20 (m, 1H), 3.13 (m, 2H), 2.63 (m, 1H), 2.58 (m, 1H),1.53 (m, 1H), 1.34 (m, 1H), 1.04 (m, 12H), 0.84 (m, 3H)

Example 5-1: Synthesis of Transition Metal Compound (Formula 2i)

2,6-diisopropyl-N-((6-(2-methyl-1,2,3,4-tetrahydroquinolin-8-yl)pyridin-2-yl)(phenyl)methyl) aniline (0.8 g, 1.634 mmol, 1 eq) which was the ligandsynthesized in c) of Example 5 was added to toluene (5.44 mL, 0.3 M) andstirred, and n-BuLi (1.3722 mL, 3.431 mmol, 2.1 eq) was added dropwise.HfCl₄ (0.549 g, 1.716 mmol, 1.05 eq) was added and the mixture washeated at 90 to 100° C. for 2 hours.

After the reaction was complete, the reaction mixture was cooled andMeMgBr (1.906 mL, 5.719 mmol, 3.5 eq, 3.0 M in DEE) was added andallowed to react at room temperature overnight. The solvent wasvacuum-dried and filtered. The celite-filtered filtrate was dried,hexane was added thereto, the mixture was stirred and vacuum-dried,pentane was further added thereto, and the mixture was stirred andvacuum-dried. When a solid was obtained, pentane was added thereto toprecipitate to obtain 430 mg of a yellow solid catalyst in a yield of41%.

¹H-NMR (toluene_d8): 7.31 (d, 1H), 7.20 (d, 1H), 7.10 (m, 9H), 6.89 (t,1H), 6.68 (t, 1H), 6.52 (d, 1H), 5.90 (s, 1H), 4.80 (s, 1H), 3.90 (m,1H), 3.04 (m, 2H), 2.61 (m, 1H), 2.19 (m, 1H), 1.80 (m, 1H), 1.45 (d,3H), 1.30 (d, 3H), 1.18 (d, 3H), 0.95 (d, 3H), 0.62 (s, 3H), 0.50 (d,3H), −0.02 (s, 3H)

Example 6: Synthesis of Ligand Compound Preparation of2,6-diisopropyl-N-((2-isopropylphenyl)(6-(2-methyl-1,2,3,4-tetrahydroquinolin-8-yl)pyridin-2-yl) methyl) Aniline

THF (13.122 mL) was added to 1-Br-2-isopropylbenzene (1.306 g, 6.561mmol, 2.7 eq), and t-BuLi (8.36 mL) was added at −78° C. The mixture wasreacted for 2 hours and the temperature was raised to room temperatureto prepare cumene lithium. Diethyl ether (24.3 mL) was added toN-(2,6-diisopropylphenyl)-1-(6-(2-methyl-1,2,3,4-tetrahydroquinolin-8-yl)pyridin-2-yl)methanimine (1 g, 2.43 mmol, 1 eq) which was the ligand precursorprepared in b) of Example 5, and the cumene lithium was added dropwiseat −78° C. The temperature was raised to room temperature, the reactionwas allowed to proceed overnight, the mixture was quenched with 1 NNH₄Cl, and then worked up with ether/H₂O. Dehydration was performedusing Na₂SO₄ and the solvent was vacuum-dried using a rotavapor. 1.48 gof yellow oil was obtained in a quantitative yield.

¹H-NMR (toluene_d8): 8.30-5.60 (m, 15H), 4.73-2.59 (m, 10H), 1.14-0.84(m, 21H)

Example 6-1: Synthesis of Transition Metal Compound (Formula 2k)

2,6-diisopropyl-N-((2-isopropylphenyl)(6-(2-methyl-1,2,3,4-tetrahydroquinolin-8-yl)pyridin-2-yl) methyl) aniline (1.21 g, 2.27 mmol, 1 eq) which was theligand prepared in Example 6 was added to toluene (7.567 mL, 0.3 M) andstirred, and n-BuLi (1.907 mL, 4.767 mmol, 2.1 eq) was added dropwise.HfCl₄ (0.7634 g, 2.3835 mmol, 1.05 eq) was added and the mixture washeated at 90 to 100° C. for 2 hours. After the reaction was complete,the reaction mixture was cooled and MeMgBr (2.65 mL, 7.945 mmol, 3.5 eq,3.0 M in DEE) was added and allowed to react at room temperatureovernight. The solvent was vacuum-dried and filtered. Thecelite-filtered filtrate was dried, hexane was added thereto, themixture was stirred and vacuum-dried, pentane was further added thereto,and the mixture was stirred and vacuum-dried. When a solid was obtained,pentane was added thereto to precipitate to obtain 320 mg of a yellowsolid catalyst in a yield of 19%.

¹H-NMR (toluene_d8): 7.34 (d, 1H), 7.32 (d, 1H), 7.20 (d, 1H), 7.12 (m,3H), 7.10 (m, 1H), 7.07 (m, 3H), 6.86 (t, 1H), 6.69 (t, 1H), 6.60 (d,1H), 6.523 (s, 1H), 4.82 (m, 1H), 3.95 (m, 1H), 3.10 (m, 1H), 3.01 (m,1H), 2.79 (m, 1H), 2.63 (m, 1H), 2.20 (m, 1H), 1.83 (m, 1H), 1.42 (d,3H), 1.31 (d, 3H), 1.13 (m, 6H), 0.93 (d, 3H), 0.71 (d, 3H), 0.65 (s,3H), 0.48 (d, 3H), 0.01 (s, 3H)

Example 7: Synthesis of Ligand Compound Preparation ofN-([1,1′-biphenyl]-2-yl(6-((S)-2-methyl-1,2,3,4-tetrahydroquinolin-8-yl)pyridin-2-yl)methyl)-2,6-diisopropyl Aniline

N-(2,6-diisopropylphenyl)-1-(6-(2-methyl-1,2,3,4-tetrahydroquinolin-8-yl)pyridin-2-yl)methanimine (1.31 g, 3.178 mmol, 1 eq) which was the ligand precursorprepared in b) of Example 5 was dissolved in diethyl ether (31.78 mL),and the temperature was lowered to −78° C. 2-Br-biphenyl (2 g, 8.580mmol, 2.7 eq) was dissolved in THF (17.16 mL) and t-BuLi (10.86 mL,17.16 mmol, 5.4 eq) was added thereto to perform a lithium substitutionreaction. When the lithium substitution reaction was complete, thereaction mixture was transferred to theN-(2,6-diisopropylphenyl)-1-(6-(2-methyl-1,2,3,4-tetrahydroquinolin-8-yl)pyridin-2-yl)methanimine solution. When the reaction was complete, the reactionmixture was quenched with 1 N NH₄Cl, and worked up with diethyl etherand water. Accordingly, 2.38 g of the product was obtained in a yield of100%.

¹H-NMR (toluene_d8): 8.50-6.64 (m, 18H), 5.50-1.48 (m, 9H), 0.9 (m, 15H)

Example 7-1: Synthesis of Transition Metal Compound (Formula 2m)

N-([1,1′-biphenyl]-2-yl(6-((S)-2-methyl-1,2,3,4-tetrahydroquinolin-8-yl)pyridin-2-yl)methyl)-2,6-diisopropyl aniline (2.38 g, 4.2064 mmol, 1 eq) prepared inExample 7 was added to toluene (14.02 mL, 0.3 M) and stirred, and n-BuLi(3.533 mL, 8.834 mmol, 2.1 eq) was added dropwise. HfCl₄ (1.415 g, 4.417mmol, 1.05 eq) was added and the mixture was heated at 90 to 100° C. for2 hours. After the reaction was complete, the reaction mixture wascooled and MeMgBr (4.907 mL, 14.72 mmol, 3.5 eq, 3.0 M in DEE) was addedand allowed to react at room temperature overnight. The solvent wasvacuum-dried and filtered. Accordingly, 290 g of the product wasobtained in a yield of 10%.

¹H-NMR (toluene_d8): 7.63 (d, 1H), 7.26 (d, 2H), 7.15 (m, 4H), 7.10 (m,2H), 7.07 (m, 4H), 7.03 (m, 3H), 6.67 (t, 2H), 6.02 (s, 1H), 4.84 (m,1H), 4.13 (m, 1H), 2.990 (m, 1H), 2.60 (m, 2H), 2.18 (m, 1H), 1.82 (m,1H), (m, 1H), 1.47 (d, 3H), 1.30 (d, 3H), 0.80 (d, 3H), 0.72 (s, 3H),0.61 (d, 3H), 0.29 (d, 3H), 0.01 (s, 3H)

Example 8: Synthesis of Ligand Compound a) Preparation ofN-(t-butyl)-1-(6-bromopyridin-2-yl) Methanimine

2-formyl-6-bromopyridine (3 g, 16.13 mmol, 1 eq), p-toluenesulfonic acid(3 drops) and a molecular sieve (1 g) were added to a Schlenk flask, andthen toluene (32.26 mL, 0.5 M) was added thereto. t-BuNH₂ (1.30 g, 17.74mmol, 1.1 eq) was added thereto, stirred overnight at 70° C., and thencooled to room temperature. After the molecular sieve was filtered, thesolvent was vacuum-dried and removed, precipitation was carried outusing cold MeOH to produce a solid, and thereby the product wasobtained. Accordingly, 3.2 g of a white solid was obtained in a yield of82.3%.

b) Preparation ofN-(t-butyl)-1-(6-(1,2,3,4-tetrahydro-2-methylquinolin-8-yl)pyridin-2-yl)Methanimine

N-(t-butyl)-1-(6-bromopyridin-2-yl) methanimine (3 g, 12.44 mmol, 1 eq)prepared as above was added to toluene (20 mL) and stirred. Meanwhile,separately, Na₂CO₃ (3.30 g, 31.1 mmol, 2.5 eq) andmethyltetrahydroquinoline-borolane (MeTHQ-borolane) (3.4 g, 12.44 mmol,1 eq) was added to a solution including H₂O (4 mL) and EtOH (4 mL) in aratio of 1:1, and stirred.

The N-(t-butyl)-1-(6-bromopyridin-2-yl) methanimine toluene solution wastransferred to the solution of Na₂CO₃ and THQ-borolane, followed by theaddition of Pd(PPh₃)₄ (0.043 g, 0.0373 mmol, 0.3 mol % Pd). The mixturewas stirred at 70° C. overnight and cooled to room temperature. Anorganic layer was extracted with toluene/brine and dehydrated withNa₂SO₄. An attempt to produce a solid using EtOH and MeOH was conducted,but the solid was not well formed, and thus the following reaction hadto proceed in a state where the starting material was included (a purityof 70%). 4 g of an orange oily product was obtained as the product in ayield of >100%.

c) Preparation of2-methyl-N-((6-(2-methyl-1,2,3,4-tetrahydro-methylquinolin-8-yl)pyridin-2-yl)(phenyl)methyl) propan-2-amine

N-(t-butyl)-1-(6-(1,2,3,4-tetrahydro-2-methylquinolin-8-yl)pyridin-2-yl)methanimine (1.17 g, 3.806 mmol, 1 eq) prepared as above was dissolvedin diethyl ether (0.1 M), the temperature was lowered to −78° C., phenyllithium (5.71 mL, 10.275 mmol, 2.7 eq) was added and then thetemperature was raised to room temperature. After a reaction wasperformed overnight, the reaction was checked by TLC and the reactionmixture was quenched with 1 N NH₄Cl and worked up with diethyl ether andwater. Dehydration was performed using Na₂SO₄ and the solvent wasvacuum-dried with a rotavapor. 1.52 g of orange oil was obtained in ayield of >100%.

¹H-NMR (toluene_d8): 8.52 (m, 12H), 5.14 (m, 1H), 3.34-1.38 (m, 6H),1.05 (s, 3H), 1.01 (s, 9H)

Example 8-1: Synthesis of Transition Metal Compound (Formula 2o)

N-((6-(1,2,3,4-tetrahydro-2-methylquinolin-8)pyridin-2-yl)(phenyl)methyl))-t-butan-1-amine (0.86 g, 2.2305 mmol, 1 eq) which was theligand synthesized in c) of Example 8 was dissolved in toluene (7.435mL, 0.3 M) and stirred, and n-BuLi (1.874 mL, 4.684 mmol, 2.1 eq) wasadded dropwise at −40° C. HfCl₄ (0.75015 g, 2.342 mmol, 1.05 eq) wasadded, and the mixture was heated at 90 to 100° C. for 2 hours.

After the reaction was complete, the reaction mixture was cooled to roomtemperature and MeMgBr (2.602 mL, 7.807 mmol, 3.5 eq, 3.0 M in DEE) wasadded and allowed to react at room temperature overnight. The solventwas vacuum-dried and then filtered. 210 mg of a brown solid product wasobtained in a yield of 16%. NMR showed the presence of the isomer.

¹H-NMR (toluene_d8): 7.40-6.60 (m, 11H), 5.84 (m, 1H), 5.00-1.8 (m, 5H),1.53-0.18 (m, 18H)

Example 9: Synthesis of Ligand Compound Preparation ofN-((2-isopropylphenyl)(6-(2-methyl-1,2,3,4-tetrahydroquinolin-8-yl)pyridin-2-yl)-2-methylpropane-2-amine

1-Br-2-isopropylbenzene (1.626 g, 8.167 mmol, 2.7 eq) was added to THF(21.38 mL), and t-BuLi (10.404 mL, 16.335 mmol, 5.4 eq) was added at−78° C. The mixture was reacted for 2 hours, and the temperature wasraised to room temperature to obtain 1-lithium-2-isopropylbenzene.

N-(t-butyl)-1-(6-(1,2,3,4-tetrahydro-2-methylquinolin-8-yl)pyridin-2-yl)methanimine which was the ligand precursor prepared in Example 17 wasdissolved in diethyl ether (30.25 mL, 0.1 M), and1-lithium-2-isopropylbenzene prepared as above was transferred thereto.After the reaction was allowed to proceed overnight at room temperature,the reaction was checked by TLC. When the reaction was complete, thereaction mixture was quenched with 1 N NH₄Cl and an organic layer wasworked up with ether/H₂O, and dehydrated with Na₂SO₄. The solvent wasvacuum-dried with a rotavapor. 1.14 g of orange oil was obtained in ayield of >100%.

¹H-NMR (toluene_d8): 8.28-6.62 (m, 11H), 5.52 (s, 1H), 3.66-1.40 (m,7H), 1.14 (s, 3H), 1.06 (s, 15H)

Example 9-1: Synthesis of Transition Metal Compound (Formula 2q)

<Synthesis of Transition Metal Compound>

N-((6-(1,2,3,4-tetrahydro-2-methylquinoline-8-yl)pyridin-2-yl)(2-isopropylphenyl)methyl)-t-butan-1-amine(1.23 g, 2.876 mmol, 1 eq) which was the ligand synthesized in Example 9was dissolved in toluene (9.587 mL, 0.3 M) and stirred, and n-BuLi(2.416 mL, 6.0401 mmol, 2.1 eq) was added dropwise at −40° C. HfCl₄(0.967 g, 3.0198 mmol, 1.05 eq) was added, and the mixture was heated at90 to 100° C. for 2 hours.

After the reaction was complete, the reaction mixture was cooled, andMeMgBr (3.355 mL, 10.066 mmol, 3.5 eq, 3.0 M in DEE) was added andallowed to react at room temperature overnight. The solvent wasvacuum-dried and then filtered. The obtained product seemed to haveseveral isomers and 588 mg of a brown solid product was obtained in ayield of 32%.

¹H-NMR (toluene_d8): 7.38-6.52 (m, 10H), 5.04-2.47 (m, 7H), 1.489-0.88(m, 24H)

Example 10: Synthesis of Ligand Compound Preparation of2,6-diisopropyl-N-((6-(2-methyl-1,2,3,4-tetrahydroquinoline-8-yl)pyridin-2-yl)(naphthyl)methyl) Aniline

N-(2,6-diisopropylphenyl)-1-(6-(2-methyl-1,2,3,4-tetrahydroquinolin-8-yl)pyridin-2-yl)methanimine (1.5 g, 3.644 mmol, 1 eq) which was the ligand precursorprepared in b) of Example 5 was dissolved in diethyl ether (36.44 mL),and the temperature was lowered to −78° C. After 1-bromonaphthalene(2.04 g, 9.84 mmol, 2.7 eq) was dissolved in THF (19.68 mL), t-BuLi(12.53 mL, 19.68 mmol, 5.4 eq) was added to perform a lithiumsubstitution reaction. When the lithium substitution reaction wascomplete, the reaction mixture was transferred to theN-(2,6-diisopropylphenyl)-1-(6-(2-methyl-1,2,3,4-tetrahydroquinolin-8-yl)pyridin-2-yl)methanimine solution. When the reaction was complete, the reactionmixture was quenched with 1 N NH₄Cl, and worked up with diethyl etherand water. Accordingly, 1.93 g of yellow oil was obtained as a productin a yield of 98%.

¹H-NMR (toluene_d8): 8.401-5.909 (m, 17H), 4.45-1.20 (10H, m), 1.09-0.38(m, 15H)

Example 10-1: Synthesis of Transition Metal Compound (Formula 2s)

2,6-diisopropyl-N-((6-(2-methyl-1,2,3,4-tetrahydroquinoline-8-yl)pyridin-2-yl)(naphthyl)methyl) aniline (1.13 g, 2.0935 mmol, 1 eq) which was the ligandprepared in Example 10 was added to toluene (6.98 mL, 0.3 M) andstirred, and n-BuLi (1.76 mL, 4.396 mmol, 2.1 eq) was added dropwise.HfCl₄ (0.704 g, 2.198 mmol, 1.05 eq) was added and the mixture washeated for 2 hours at 90 to 100° C.

After the reaction was complete, the reaction mixture was cooled, andMeMgBr (2.44 mL, 7.33 mmol, 3.5 eq, 3.0 M in DEE) was added and allowedto react at room temperature overnight. The solvent was vacuum-dried andthen filtered. 210 mg of a yellow solid product was obtained in a yieldof 13%.

¹H-NMR (toluene_d8): 7.60-6.38 (m, 16H), 4.87 (m, 1H), 3.27-1.81 (m,7H), 1.30-0.0 (m, 2H)

Example 11: Synthesis of Ligand Compound Preparation of2,6-diisopropyl-N-((6-(2-methyl-1,2,3,4-tetrahydroquinoline-8-yl)pyridin-2-yl)(4-tert-butylphenyl)methyl)Aniline

N-(2,6-diisopropylphenyl)-1-(6-(2-methyl-1,2,3,4-tetrahydroquinolin-8-yl)pyridin-2-yl)methanimine (2.146 g, 5.215 mmol, 1 eq) which was the ligand precursorprepared in b) of Example 5 was dissolved in diethyl ether (52.15 mL),and the temperature was lowered to −78° C. After1-tert-butyl-4-bromophenyl (3 g, 14.08 mmol, 2.7 eq) was dissolved inTHF (28.16 mL), t-BuLi (17.82 mL, 28.161 mmol, 5.4 eq) was added toperform a lithium substitution reaction. When the lithium substitutionreaction was complete, the reaction mixture was transferred to theN-(2,6-diisopropylphenyl)-1-(6-(2-methyl-1,2,3,4-tetrahydroquinolin-8-yl)pyridin-2-yl)methanimine solution. When the reaction was complete, the reactionmixture was quenched with 1 N NH₄Cl, and worked up with diethyl etherand water. Accordingly, 2.0 g of orange solid was obtained as theproduct in a yield of 70%.

¹H-NMR (toluene_d8): 8.23-6.64 (m, 14H), 5.33-1.50 (m, 9H), 1.21-0.99(m, 24H)

Example 11-1: Synthesis of Transition Metal Compound (Formula 2u)

2,6-diisopropyl-N-((6-(2-methyl-1,2,3,4-tetrahydroquinoline-8-yl)pyridin-2-yl)(4-tert-butylphenyl)methyl)aniline(1 g, 1.832 mmol, 1 eq) which was the ligand prepared in Example 11 wasadded to toluene (6.107 mL, 0.3 M) and stirred, and n-BuLi (1.539 mL,3.847 mmol, 2.1 eq) was added dropwise. HfCl₄ (0.616 g, 1.9236 mmol,1.05 eq) was added thereto, and the mixture was heated at 90 to 100° C.for 2 hours.

After the reaction was complete, the reaction mixture was cooled, andMeMgBr (2.137 mL, 6.412 mmol, 3.5 eq, 3.0 M in DEE) was added andallowed to react at room temperature overnight. The solvent wasvacuum-dried and then filtered. 1.04 g of a red solid product wasobtained in a yield of 75%.

¹H-NMR (toluene_d8): 7.32-5.93 (m, 13H), 4.81-1.80 (m, 8H), 1.15-0.00(m, 30H)

Example 1-A: Preparation of Ethylene-Octene Copolymer

A hexane solvent (1.0 L), octene (280 mL) and ethylene (35 bar) wereadded to a 2 L autoclave reactor, a pressure was set as 500 psi usinghigh argon pressure, and the temperature of the reactor was pre-heatedto 120° C. 10 equivalents of a 5×10⁻⁶ M dimethylaniliniumtetrakis(pentafluorophenyl)borate cocatalyst was added in the reactorwhile applying high argon pressure, and the transition metal compound(1×10⁻⁶ M, 2.0 mL) of Example 1-1 treated with a triisobutyl aluminumcompound was placed in a catalyst storage tank and added in the reactorwhile applying high argon pressure. The polymerization reaction wasperformed for 10 minutes. The reaction heat was removed through acooling coil inside the reactor to maintain the polymerizationtemperature as constant as possible. After the polymerization reactionproceeded for 10 minutes, a residual gas was exhausted, and a polymersolution was discharged to the lower part of the reactor, and anexcessive amount of ethanol was added thereto to induce precipitation.The obtained polymer was washed with ethanol and acetone twice and threetimes, respectively, and was dried in a vacuum oven at 90° C. for atleast 12 hours to prepare an ethylene-octene copolymer.

Example 1-B, 2-A to 11-A: Preparation of Ethylene-Octene Copolymer

An ethylene-octene copolymer was prepared in the same manner as inExample 1-A except that each transition metal compound as shown in thefollowing Table 6 was treated with a triisobutyl aluminum compound andused instead of the transition metal compound of Example 1-1 treatedwith the triisobutyl aluminum compound in Example 1-A.

Experimental Example 1: Measurement of Catalytic Activity

The catalyst activity in the preparation of the copolymers in Examples1-A to 7-A, 10-A and 11-A was measured by the following method, and theresults are shown in Table 6 below.

The catalytic activity was calculated using the molar ratio of thetransition metal compound to the total yield of the prepared copolymer.Specifically, the ratio of a value obtained by measuring the mass of apart of the reaction solution taken after completion of thepolymerization reaction to a value obtained by heating a part of thecopolymer at 120° C. for 10 minutes to remove both the hexane solventand the residual monomer and measuring the mass of the remainingcopolymer was calculated. Based on this, the catalytic activity wascalculated using the mass of the resulting copolymer, the number ofmoles of the transition metal compound used in the polymerizationreaction, and the polymerization time.

TABLE 6 Transition metal Catalytic activity compound (KgPE/mmol) Example1-A Example 1-1 2.7 Example 1-B Example 1-2 0.8 Example 2-A Example 2-15.6 Example 2-B Example 2-2 0.74 Example 3-A Example 3-1 1.0 Example 4-AExample 4-1 2.2 Example 5-A Example 5-1 2.3 Example 6-A Example 6-1 5.3Example 7-A Example 7-1 2.7 Example 10-A Example 10-1 2.3 Example 11-AExample 11-1 1.5

As can be seen in Table 6, the transition metal compounds of Examples1-1 to 7-1, 10-1, and 11-1 exhibited catalytic activity in thepreparation of the ethylene-octene copolymer.

Experimental Example 2: Measurement of Physical Properties

The melt index (MI), density, and melting point of the polymers preparedin Examples 6-A, 7-A and 10A were measured by the following methods, andthe results are shown in Table 7 below.

(1) The melt index (MI) of the polymer was measured by ASTM D-1238(condition E, 190° C., a load of 2.16 kg).

(2) The density of the polymer was measured by ASTM D-792.

(3) The melting point (Tm) was measured using Q100 manufactured by TACo.

TABLE 7 Transition Catalytic Melting metal activity MT Density pointcompound (KgPE/mmol) (g/10 min) (g/cc) (° C.) Example Example 6-1 5.30.02 0.865 50.3 6-A Example Example 7-1 2.7 0.02 0.883 72.9 7-A ExampleExample 2.3 0.01 0.873 60.9 10-A 10-1

As can be seen Table 7, polymers of Examples 6-A, 7-A and 10A preparedusing the transition metal compound of Examples 6-1, 7-1, and 10-1 whichare examples of the transition metal compound of the present inventionshowed a low melt index (MI) of 0.02 or less, which indicates a highmolecular weight, and a density of 0.883 g/cc or less. Particularly,polymers of Examples 6-A and 10-A prepared using the transition metalcompounds of Examples 6-1 and 10-1 showed a low density of 0.873 g/cc orless and a low melt index (MI) of 0.02 or less, which indicate a lowdensity and a high molecular weight.

The invention claimed is:
 1. A ligand compound represented by thefollowing Formula 1:

in Formula 1, R₁ to R₉ each independently represent hydrogen, a silyl,an alkyl having 1 to 20 carbon atoms, an alkenyl having 2 to 20 carbonatoms, an aryl having 6 to 20 carbon atoms, an alkylaryl having 7 to 20carbon atoms, an arylalkyl having 7 to 20 carbon atoms or a metalloidradical of a Group 14 metal substituted with a hydrocarbyl having 1 to20 carbon atoms; two or more adjacent groups of the R₁ to R₈ areoptionally connected to each other to form an aliphatic ring having 5 to20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; thealiphatic ring or aromatic ring is optionally substituted with ahalogen, an alkyl having 1 to 20 carbon atoms, an alkenyl having 2 to 20carbon atoms or an aryl having 6 to 20 carbon atoms; and n is 1 or
 2. 2.The ligand compound according to claim 1, wherein, in Formula 1, R₁ toR₉ each independently represent hydrogen, an alkyl having 1 to 20 carbonatoms, an aryl having 6 to 20 carbon atoms, an alkylaryl having 7 to 20carbon atoms, or an arylalkyl having 7 to 20 carbon atoms; two or moreadjacent groups of the R₁ to R₈ are optionally connected to each otherto form an aliphatic ring having 5 to 20 carbon atoms or an aromaticring having 6 to 20 carbon atoms; and the aliphatic ring or aromaticring is optionally substituted with a halogen, an alkyl having 1 to 20carbon atoms, or an aryl having 6 to 20 carbon atoms.
 3. The ligandcompound according to claim 1, wherein the compound of Formula 1 is oneof the following compounds: